Chlorinated polyethylene rubber material, preparation method thereof and application of chlorinated polyethylene rubber material in preparation of turbocharging pipe

Abstract

The invention provides a chlorinated polyethylene rubber material, a preparation method thereof and application of the chlorinated polyethylene rubber material in preparation of turbocharging pipes, and relates to the technical field of turbocharging pipes, the chlorinated polyethylene rubber material comprises the following components: chlorinated polyethylene rubber, a composite scorch retarder, an alkaline metal oxide, a thiadiazole vulcanizing agent and an amine accelerator; the composite scorch retarder is prepared from the following components: N-cyclohexylthiophthalimide, benzenesulfonamide and an antioxidant. According to the chlorinated polyethylene rubber material provided by the invention, a new thiadiazole vulcanization system is adopted, and the composite scorch retarder is introduced to prolong the scorch time, so that the extrusion process requirements are met. The ozone resistance and the mechanical property of chlorinated polyethylene rubber are improved, the problem of scabbing in the vulcanization process of the CM rubber tube is solved, the cleaning frequency of the core rod is reduced, the production efficiency is improved, and the labor cost is reduced.

Description

Technical Field

[0001] This invention relates to the field of turbocharger pipe technology, and in particular to a chlorinated polyethylene rubber material, its preparation method, and its application in the preparation of turbocharger pipes. Background Technology

[0002] Chlorinated polyethylene rubber (CM) is a synthetic elastomer with excellent oil resistance, heat resistance and good flame retardancy. Due to its excellent comprehensive properties, it has a wide range of applications in automobiles, construction, industrial equipment and other fields.

[0003] Currently, commonly used vulcanization systems for CM (Chemical Molding) include thiourea, peroxide, and thiadiazole. Among these, the peroxide vulcanization system is widely used in existing rubber hose products due to its mature vulcanization process and controllable crosslinking density. However, in practical applications, it has been found that this vulcanization system has significant defects under high ozone concentrations and dynamic stress. CM rubber products prepared using the peroxide vulcanization system exhibit poor ozone aging resistance and are prone to surface cracking, affecting product lifespan and reliability. Furthermore, the peroxide vulcanization process generates small-molecule byproducts with irritating odors, such as acetylbenzene. Additionally, residual polymerization solvents in the raw rubber, non-environmentally friendly plasticizers, and polycyclic aromatic hydrocarbons (such as anthracene and naphthalene) that may be present in the carbon black further contribute to the release of volatile organic compounds (VOCs) and odorous substances during processing and use, posing potential impacts on human health and the environment. This is especially problematic in enclosed spaces such as car cabins, where it can significantly affect driver comfort and experience. In addition, CM rubber hoses or molded products often cause mold contamination and difficulty in demolding during the vulcanization process. CM hoses also have scab formation on the inner wall during vulcanization, which increases the frequency of cleaning the mandrel in the workshop, reduces production efficiency, and increases labor costs.

[0004] In comparison, the thiadiazole vulcanization system exhibits superior ozone aging resistance and mechanical properties, and the vulcanization process is relatively clean, with low odor and minimal pollution. However, due to its rapid vulcanization reaction, this system is prone to scorching during extrusion processing, resulting in poor process stability and limiting its widespread application in actual production.

[0005] In view of this, the present invention is hereby proposed. Summary of the Invention

[0006] One objective of this invention is to provide a chlorinated polyethylene rubber material to at least solve one of the technical problems existing in the prior art. The chlorinated polyethylene rubber material provided by this invention employs a novel thiadiazole vulcanization system, introduces a composite anti-scorching agent to extend the scorching time, and meets the requirements of the extrusion process. It improves the ozone resistance and mechanical properties of chlorinated polyethylene rubber, solves the scabbing problem during the vulcanization of CM hoses, reduces the frequency of mandrel cleaning, improves production efficiency, and reduces labor costs.

[0007] The second objective of this invention is to provide a method for preparing chlorinated polyethylene rubber material.

[0008] A third objective of this invention is to provide an application of chlorinated polyethylene rubber material or chlorinated polyethylene rubber material prepared by the aforementioned preparation method in the preparation of turbocharger pipes.

[0009] The fourth objective of this invention is to provide a turbocharger pipe.

[0010] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted:

[0011] In a first aspect, the present invention provides a chlorinated polyethylene rubber material, the components of which include: chlorinated polyethylene rubber, a composite anti-scorching agent, an alkaline metal oxide, a thiadiazole vulcanizing agent, and an amine accelerator;

[0012] The composite anti-scorching agent comprises: N-cyclohexylthiophthalimide, benzenesulfonamide, and antioxidant.

[0013] Furthermore, the alkaline metal oxide includes one or both of magnesium oxide and zinc oxide;

[0014] Preferably, the thiadiazole vulcanizing agent includes one or more of JY-75, PT-75, TDD, TDDS, and the composite vulcanizing agent H631;

[0015] Preferably, the amine accelerator includes one or both of JY719 and accelerator 903.

[0016] Furthermore, the components of the chlorinated polyethylene rubber material also include: carbon black, filler, plasticizer, and flow aid;

[0017] Preferably, the filler comprises one or both of N85 and H1010;

[0018] Preferably, the plasticizer includes one or more of TOTM, epoxy fatty acid methyl esters, and citrate esters;

[0019] Preferably, the flow aid includes one or both of WB222 and LP-54;

[0020] Preferably, the antioxidant includes hindered phenolic antioxidants and / or phosphite antioxidants.

[0021] Furthermore, the components of the chlorinated polyethylene rubber material, by weight fraction, include: 100 parts chlorinated polyethylene rubber, 30-50 parts carbon black, 10-20 parts filler, 30-50 parts plasticizer, 0.5-1.5 parts composite anti-scorching agent, 6-15 parts alkaline metal oxide, 1-5 parts flow aid, 1.0-3.0 parts thiadiazole vulcanizing agent, and 0.5-1.5 parts amine accelerator.

[0022] Furthermore, the composite anti-scorching agent comprises, by weight percentage: 30%-40% benzenesulfonamide, 20%-30% hindered phenolic antioxidant, 15%-25% phosphite antioxidant, and the balance N-cyclohexylthiophthalimide.

[0023] Secondly, the present invention provides a method for preparing chlorinated polyethylene rubber material, comprising the following steps:

[0024] (a) A mixture of chlorinated polyethylene rubber, composite anti-scorching agent and alkaline metal oxide is mixed once to obtain a compound rubber.

[0025] (b) Add thiadiazole vulcanizing agent and amine accelerator to the first-stage compound and perform secondary mixing to obtain the chlorinated polyethylene rubber material.

[0026] Furthermore, the preparation process of the composite anti-scorching agent includes: mixing N-cyclohexylthiophthalimide, benzenesulfonamide and antioxidant to obtain the composite anti-scorching agent;

[0027] Preferably, the mixture in step (a) further includes carbon black, filler, plasticizer and flow aid.

[0028] Thirdly, the present invention provides an application of chlorinated polyethylene rubber material or chlorinated polyethylene rubber material prepared by the aforementioned preparation method in the preparation of turbocharger pipes.

[0029] Fourthly, the present invention provides a turbocharger pipe, comprising: an inner adhesive layer, a reinforcing layer, and an outer adhesive layer;

[0030] Both the inner and outer rubber layers are made of the chlorinated polyethylene rubber material or chlorinated polyethylene rubber material prepared by the preparation method described above.

[0031] The reinforcing layer is disposed on the outside of the inner adhesive layer, and the outer adhesive layer is disposed on the outside of the reinforcing layer.

[0032] Furthermore, the material of the reinforcing layer includes aramid yarns;

[0033] Preferably, the preparation process of the turbocharger pipe includes: forming an inner rubber layer by extrusion using chlorinated polyethylene rubber material, then forming a reinforcing layer by knitting aramid yarn on the inner rubber layer, and then forming an outer rubber layer by extrusion using chlorinated polyethylene rubber material on the surface of the reinforcing layer;

[0034] Preferably, after forming the inner adhesive layer, the reinforcing layer, and the outer adhesive layer, cooling is performed to obtain the tube blank;

[0035] Preferably, the tube blank is vulcanized to obtain a turbocharger tube.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] The chlorinated polyethylene rubber material provided by this invention employs a composite anti-scorching agent, with N-cyclohexylthiophthalimide (CTP) as the main anti-scorching agent. By capturing active sulfur free radicals in the vulcanization reaction, it delays the initiation of the vulcanization reaction and effectively prevents premature vulcanization (scorching) of the rubber compound during mixing and extrusion. Benzenesulfonamide is used as an auxiliary anti-scorching agent, working synergistically with CTP to enhance the anti-scorching effect and regulate the vulcanization speed. Antioxidants are also added, working synergistically with CTP and benzenesulfonamide to prevent early vulcanization or performance degradation caused by oxidation. Therefore, the composite anti-scorching agent can effectively extend the scorching time of the thiadiazole vulcanization system, meeting the requirements of the extrusion process.

[0038] Furthermore, the chlorinated polyethylene rubber material provided by this invention also includes thiadiazole vulcanizing agents, amine accelerators, and alkaline metal oxides. These components constitute a thiadiazole derivative vulcanization system. The crosslinking bonds formed in this system are primarily carbon-sulfur (CS) and sulfur-sulfur (SS) bonds. These bonds exhibit high chemical stability, effectively resisting ozone erosion and forming a dense crosslinked network. This structure effectively prevents ozone molecules from penetrating the rubber interior, thus delaying ozone aging. The rubber vulcanized using the thiadiazole vulcanization system exhibits high tear strength, a physical property that effectively resists surface crack propagation caused by ozone aging. Additionally, the thiazolium thiazole groups in the thiadiazole vulcanizing agent exhibit highly acidic protons. Therefore, upon reaction with an alkali, they generate sulfur cations, which crosslink with the carbon-chlorine bonds of chlorinated polyethylene, replacing the chlorine and forming carbon-sulfur bonds. This crosslinking process does not produce irritating odor substances, reducing VOC emissions and optimizing product odor. Meanwhile, the vulcanization reaction path of the thiadiazole vulcanization system is different from that of the peroxide system, avoiding the chemical reaction between the release agent and the components of the vulcanization system, thereby inhibiting the formation of scab. In addition, the present invention introduces a composite anti-scorching agent, which can improve the thermal stability of the rubber compound during the vulcanization process, reduce local over-vulcanization reaction, and further reduce the tendency to scab. Therefore, it can significantly reduce the scab phenomenon on the inner wall of the hose, improve the release performance of the mandrel, reduce the frequency of mandrel cleaning, and improve production efficiency. Attached Figure Description

[0039] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0040] Figure 1 This is a schematic diagram of the structure of the turbocharger pipe provided by the present invention. Detailed Implementation

[0041] Unless otherwise defined herein, the scientific and technical terms used in conjunction with this invention shall have the meanings commonly understood by one of ordinary skill in the art. The meaning and scope of terms shall be clear; however, in any case of potential ambiguity, the definitions provided herein shall prevail over any dictionary or foreign definitions. In this application, unless otherwise stated, the use of "or" means "and / or". Furthermore, the use of the term "comprising" and other forms is non-limiting.

[0042] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0043] The first aspect of this invention provides a chlorinated polyethylene rubber material, the components of which include: chlorinated polyethylene rubber, a composite anti-scorching agent, an alkaline metal oxide, a thiadiazole vulcanizing agent, and an amine accelerator;

[0044] The composite anti-scorching agent comprises: N-cyclohexylthiophthalimide, benzenesulfonamide, and antioxidant.

[0045] In some preferred embodiments, the antioxidant includes hindered phenolic antioxidants and / or phosphite antioxidants.

[0046] In this invention, a combination of hindered phenolic antioxidants and phosphite antioxidants is preferably used to form a composite anti-aging system. The hindered phenolic antioxidants can inhibit oxidative aging and, in synergy with phosphite, enhance thermal stability and storage stability. The phosphite antioxidants can decompose peroxides and form a composite antioxidant system with the hindered phenols, thus extending the life of the rubber compound.

[0047] This invention employs a novel thiadiazole vulcanization system, introducing a composite anti-scorching agent to extend the scorching time, reduce Mooney viscosity, and meet extrusion requirements, thus solving the problem of rapid scorching and unsatisfactory extrusion performance in thiadiazole vulcanization. This provides strong support for the application of thiadiazole vulcanization systems.

[0048] Furthermore, this invention uses low-odor chlorinated polyethylene rubber. The chlorinated polyethylene rubber (e.g., CH-430) produced during the synthesis and processing via aqueous suspension and continuous methods essentially removes organic solvents from the production process, achieving a chlorine distribution uniformity of over 99%, better batch stability and performance, and does not produce irritating odor substances during crosslinking, thus reducing VOC emissions and optimizing product odor.

[0049] In some preferred embodiments, the alkaline metal oxide includes one or both of magnesium oxide and zinc oxide; magnesium oxide is preferred.

[0050] Preferably, the thiadiazole vulcanizing agent includes one or more of JY-75, PT75, TDD, TDDS, and the composite vulcanizing agent H631;

[0051] Preferably, the amine accelerator includes one or both of JY719 and accelerator 903.

[0052] In some preferred embodiments, the chlorinated polyethylene rubber material further includes: carbon black, filler, plasticizer, and flow aid.

[0053] Preferably, the filler comprises one or both of N85 and H1010;

[0054] Preferably, the plasticizer includes one or more of TOTM (trioctyl trimellitate), epoxy fatty acid methyl ester, and citrate ester;

[0055] Preferably, the flow aid includes one or both of WB222 and LP-54.

[0056] In this invention, carbon black, fillers, plasticizers, and flow aids are added to the chlorinated polyethylene rubber material component. Carbon black is used as a rubber reinforcing filler to improve the mechanical properties of the rubber. The fillers in this invention include N85 and / or H1010, which are functional fillers that not only provide physical filling but also have chemical anti-aging functions. Plasticizers can improve the plasticity and flexibility of the rubber compound, reduce Mooney viscosity, and improve extrudability by improving the flowability and processability of the rubber. Flow aids can improve the extrudability and release properties of the rubber compound.

[0057] The thiadiazole derivative vulcanization system of this invention is composed of an amine accelerator, a thiadiazole derivative (vulcanizing agent), and an alkaline metal oxide. The preferred thiadiazole vulcanizing agent is JY75, which participates in the vulcanization reaction as a crosslinking agent. The preferred amine accelerator is JY719, which is used to accelerate the crosslinking reaction between the thiadiazole derivative and CM and can work synergistically with the thiadiazole derivative to improve the vulcanization efficiency. The alkaline metal oxide provides an alkaline environment to promote the crosslinking reaction between the thiadiazole derivative and CM.

[0058] Unlike peroxide systems, thiadiazole derivative vulcanization systems do not produce irritating odors and can improve the ozone resistance of chlorinated polyethylene. Under high-concentration dynamic ozone conditions, peroxide-vulcanized rubber compounds exhibit worse ozone resistance than thiadiazole-vulcanized compounds. This is because peroxide-vulcanized systems readily generate free radicals under prolonged high-temperature conditions. These free radicals abstract hydrogen atoms from the chlorinated polyethylene molecular chain, forming macromolecular free radicals. These macromolecular free radicals undergo β-elimination reactions, losing one chlorine atom and one hydrogen atom to form carbon-carbon double bonds (C=C). These double bonds are easily broken under ozone conditions, leading to cracking on the rubber surface. Furthermore, peroxide-vulcanized systems primarily form C=C bonds. While these bonds have high chemical stability, they have poor tear resistance and are prone to breakage under dynamic stress conditions, allowing ozone molecules to penetrate more easily into the rubber and trigger crack propagation. Thiadiazole vulcanization, as demonstrated by tube grinding disc tests, shows superior performance. The main advantage lies in the fact that the cross-linking bonds formed by the thiadiazole derivative vulcanization system are primarily carbon-sulfur bonds (CS) and sulfur-sulfur bonds (SS). These bonds possess high chemical stability, effectively resisting ozone erosion. Simultaneously, they form a dense cross-linked network, which effectively prevents ozone molecules from penetrating into the rubber interior, thus delaying ozone aging. The rubber vulcanized using the thiadiazole vulcanization system exhibits high tear strength, a physical property that effectively resists surface crack propagation caused by ozone aging. Therefore, the chlorinated polyethylene rubber material provided by this invention can improve ozone resistance and mechanical properties, solving the problem of pipe cracking. Furthermore, since crusting is mainly due to the fact that chlorinated polyethylene is a non-polar rubber, and the release agent contains polar silane coupling agents, these components migrate to the rubber surface during vulcanization, reacting with peroxides and accelerators to produce insoluble substances, resulting in crusting. The thiadiazole vulcanization system used in this invention, compared to existing peroxide vulcanization systems for chlorinated polyethylene, solves the problem of crusting on the inner wall of the product during vulcanization, reduces the frequency of mandrel cleaning, significantly improves production efficiency, saves labor costs, and enhances product competitiveness.

[0059] In some preferred embodiments, the components of the chlorinated polyethylene rubber material, by weight fraction, include: 100 parts chlorinated polyethylene rubber, 30-50 parts carbon black, 10-20 parts filler, 30-50 parts plasticizer, 0.5-1.5 parts composite anti-scorching agent, 6-15 parts alkaline metal oxide, 1-5 parts flow aid, 1.0-3.0 parts thiadiazole vulcanizing agent, and 0.5-1.5 parts amine accelerator.

[0060] In the chlorinated polyethylene rubber material, the amount of carbon black added is 30 to 50 parts by weight fraction, for example, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, etc.

[0061] In the chlorinated polyethylene rubber material, the amount of filler added is 10 to 20 parts by weight fraction, for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, etc.

[0062] In the chlorinated polyethylene rubber material, the amount of plasticizer added is 30 to 50 parts by weight fraction, for example, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, etc.

[0063] In the chlorinated polyethylene rubber material, the amount of composite anti-scorching agent added is 0.5 to 1.5 parts by weight, for example, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, etc.; the composite anti-scorching agent is further preferably 0.5-1.2 parts.

[0064] In the chlorinated polyethylene rubber material, the amount of alkaline metal oxide added is 6 to 15 parts by weight fraction, for example, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, etc.

[0065] In the chlorinated polyethylene rubber material, the amount of flow aid added is 1 to 5 parts by weight fraction, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, etc.

[0066] In the chlorinated polyethylene rubber material, the amount of thiadiazole vulcanizing agent added is 1.0 to 3.0 parts by weight, for example, 1 part, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, etc.

[0067] In the chlorinated polyethylene rubber material, the amount of amine accelerator added is 0.5 to 1.5 parts by weight, for example, 0.5 parts, 1 part, 1.5 parts, etc.

[0068] In some preferred embodiments, the composite anti-scorching agent comprises, by weight percentage: 30%-40% benzenesulfonamide, 20%-30% hindered phenolic antioxidant, 15%-25% phosphite antioxidant, and the balance N-cyclohexylthiophthalimide.

[0069] Among them, based on the total weight of the composite anti-scorching agent as 100%, the amount of benzenesulfonamide added is 30%-40%, for example, it can be 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, etc.;

[0070] Among them, based on the total weight of the composite anti-scorching agent as 100%, the amount of hindered phenolic antioxidant added is 20%-30%, for example, it can be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, etc.

[0071] Among them, based on the total weight of the composite anti-scorching agent as 100%, the amount of phosphite antioxidant added is 15%-25%, for example, it can be 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, etc.

[0072] A second aspect of this invention provides a method for preparing chlorinated polyethylene rubber material, comprising the following steps:

[0073] (a) A mixture of chlorinated polyethylene rubber, composite anti-scorching agent and alkaline metal oxide is mixed once (process conditions: mixing temperature not higher than 120℃, mixing pressure 3-5MPa, mixing time 5-8 minutes) to obtain a first-stage compound;

[0074] (b) Add thiadiazole vulcanizing agent and amine accelerator to the first-stage compound and perform secondary mixing (process conditions: mixing temperature not higher than 100℃, mixing pressure 3-5MPa, mixing time 2-4 minutes) to obtain the chlorinated polyethylene rubber material.

[0075] In some preferred embodiments, the preparation process of the composite anti-scorching agent includes: mixing N-cyclohexylthiophthalimide, benzenesulfonamide and antioxidant to obtain the composite anti-scorching agent;

[0076] Preferably, the mixture in step (a) further includes carbon black, filler, plasticizer and flow aid.

[0077] The third aspect of this invention provides the application of a chlorinated polyethylene rubber material or a chlorinated polyethylene rubber material prepared by the aforementioned preparation method in the preparation of turbocharger pipes.

[0078] like Figure 1 As shown, a fourth aspect of the present invention provides a turbocharger pipe, comprising: an inner rubber layer, a reinforcing layer, and an outer rubber layer; the materials of the inner rubber layer and the outer rubber layer both include the chlorinated polyethylene rubber material described above or the chlorinated polyethylene rubber material prepared by the preparation method described above;

[0079] The inner adhesive layer, the reinforcing layer, and the outer adhesive layer are all tubular structures. The reinforcing layer is located outside the inner adhesive layer, and the outer adhesive layer is located outside the reinforcing layer.

[0080] In some preferred embodiments, the reinforcing layer is made of aramid yarn (AR);

[0081] Preferably, the preparation process of the turbocharger pipe includes: forming an inner rubber layer by extrusion using chlorinated polyethylene rubber material, then forming a reinforcing layer by knitting aramid yarn on the inner rubber layer, and then forming an outer rubber layer by extrusion using chlorinated polyethylene rubber material on the surface of the reinforcing layer;

[0082] Preferably, after forming the inner adhesive layer, the reinforcing layer, and the outer adhesive layer, cooling is performed to obtain the tube blank;

[0083] Preferably, the tube blank is vulcanized to obtain a turbocharger tube.

[0084] This invention employs a thiadiazole vulcanization system, which solves the problems of difficult demolding and scab formation on the inner wall of the tubing during vulcanization. Scab formation is primarily due to the fact that chlorinated polyethylene is a non-polar rubber, while the release agent contains polar components, such as silane coupling agents. During vulcanization, these components migrate to the rubber surface, react with peroxides and accelerators, and produce insoluble substances, resulting in scab formation. Because the thiadiazole vulcanization system is used for extruded CM / AR / CM products, scab formation does not occur even if the release agent migrates to the rubber surface during vulcanization. Therefore, the frequency of mandrel cleaning is reduced after vulcanization, improving production efficiency and lowering labor costs.

[0085] The turbocharger pipe provided by this invention is a turbocharger pipe with high ozone resistance and low odor.

[0086] This invention also proposes a method for evaluating ozone performance. It uses an external rubber grinding disc with a sample size of 10mm×100mm×1.5mm and a high ozone concentration of 200pphm under dynamic conditions. This method can reproduce the cracking phenomenon reported in the market and effectively combine the actual use of the product with the experiment. This results in an effective method for evaluating the ozone resistance of CM rubber compounds, providing support for the research and development of CM rubber compounds.

[0087] The present invention will be further illustrated by the following examples. Unless otherwise specified, the materials in the examples are prepared according to existing methods or purchased directly from the market.

[0088] In the following examples and comparative examples, 1 part is 1g.

[0089] Example 1

[0090] This embodiment provides a chlorinated polyethylene rubber material, which, by weight percentage, comprises the following components:

[0091] 100 parts chlorinated polyethylene rubber (CH-430), 40 parts carbon black (N550), 15 parts filler (N85), 35 parts plasticizer (TOTM), 1 part composite anti-scorching agent, 12 parts magnesium oxide, 3 parts flow aid (WB222), 2 parts thiadiazole vulcanizing agent JY75 and 1 part amine accelerator JY719;

[0092] The composite anti-scorching agent includes 20% N-cyclohexylthiophthalimide (CTP), 35% benzenesulfonamide EC-80, 25% hindered phenol 168 and 20% phosphite.

[0093] The preparation process of chlorinated polyethylene rubber material is as follows:

[0094] Step 1: First, mix and compound the CTP, benzenesulfonamide EC-80, hindered phenol 168, and phosphite in the specified amounts to obtain a composite anti-scorching agent;

[0095] Step 2: Add the chlorinated polyethylene rubber, carbon black, filler N85, plasticizer TOTM, composite anti-scorching agent, magnesium oxide and flow aid to the internal mixer in sequence. Mix once at a mixing temperature not higher than 120℃, a mixing pressure of 4MPa and a mixing time of 7 minutes to obtain a compound rubber.

[0096] Step 3: Add vulcanizing agent JY75 and accelerator JY719, and perform secondary mixing. The mixing temperature should not exceed 100℃, the mixing pressure should be 4MPa, and the mixing time should be 3 minutes. The secondary mixing will yield CM rubber compound (chlorinated polyethylene rubber material).

[0097] Example 2

[0098] This embodiment provides a chlorinated polyethylene rubber material, which differs from Embodiment 1 in that the composite anti-scorching agent in the chlorinated polyethylene rubber material is 0.5 parts;

[0099] The remaining components and the preparation method of the chlorinated polyethylene rubber material are the same as in Example 1.

[0100] Example 3

[0101] This embodiment provides a chlorinated polyethylene rubber material, which differs from Embodiment 1 in that the composite anti-scorching agent in the chlorinated polyethylene rubber material is 1.2 parts;

[0102] The remaining components and the preparation method of the chlorinated polyethylene rubber material are the same as in Example 1.

[0103] Example 4

[0104] This embodiment provides a chlorinated polyethylene rubber material, which differs from Embodiment 1 in that the composite anti-scorching agent in the chlorinated polyethylene rubber material is 1.5 parts;

[0105] The remaining components and the preparation method of the chlorinated polyethylene rubber material are the same as in Example 1.

[0106] Example 5

[0107] This embodiment provides a chlorinated polyethylene rubber material, which differs from Embodiment 1 in that: the composite anti-scorching agent includes 5% N-cyclohexylthiophthalimide (CTP), 40% benzenesulfonamide EC-80, 30% hindered phenol 168 and 25% phosphite.

[0108] The remaining components and the preparation method of the chlorinated polyethylene rubber material are the same as in Example 1.

[0109] Example 6

[0110] This embodiment provides a chlorinated polyethylene rubber material, which differs from Embodiment 1 in that: the composite anti-scorching agent includes 35% N-cyclohexylthiophthalimide (CTP), 30% benzenesulfonamide EC-80, 20% hindered phenol 168 and 15% phosphite.

[0111] The remaining components and the preparation method of the chlorinated polyethylene rubber material are the same as in Example 1.

[0112] Example 7

[0113] This embodiment provides a chlorinated polyethylene rubber material, which differs from Embodiment 1 in that: the composite anti-scorching agent includes 50% N-cyclohexylthiophthalimide (CTP), 25% benzenesulfonamide EC-80, 15% hindered phenol 168 and 10% phosphite.

[0114] The remaining components and the preparation method of the chlorinated polyethylene rubber material are the same as in Example 1.

[0115] Example 8

[0116] This embodiment provides a chlorinated polyethylene rubber material, which differs from Embodiment 1 in that: the composite anti-scorching agent includes 15% N-cyclohexylthiophthalimide (CTP), 45% benzenesulfonamide EC-80, 35% hindered phenol 168 and 5% phosphite.

[0117] The remaining components and the preparation method of the chlorinated polyethylene rubber material are the same as in Example 1.

[0118] Example 9

[0119] This embodiment provides a chlorinated polyethylene rubber material, which differs from Embodiment 1 in that:

[0120] In the composition of chlorinated polyethylene rubber material, 1 part of thiadiazole vulcanizing agent JY75 and 1.5 parts of amine accelerator JY719 are present.

[0121] The remaining components and the preparation method of the chlorinated polyethylene rubber material are the same as in Example 1.

[0122] Example 10

[0123] This embodiment provides a chlorinated polyethylene rubber material, which differs from Embodiment 1 in that:

[0124] The chlorinated polyethylene rubber material contains 3 parts of thiadiazole vulcanizing agent JY75 and 0.5 parts of amine accelerator JY719.

[0125] The remaining components and the preparation method of the chlorinated polyethylene rubber material are the same as in Example 1.

[0126] Application Example 1-10

[0127] This application example provides a turbocharger pipe, the preparation method of which is as follows:

[0128] Application Examples 1-10 respectively use the CM rubber compound prepared in Examples 11-20 to extrude the inner rubber layer, knit the reinforcing aramid yarn on the inner layer, and then use the CM rubber compound prepared in Examples 11-20 to extrude the outer tube (i.e. the outer rubber layer) on the surface of the reinforcing layer, cool, and obtain the tube blank; then perform a vulcanization to obtain a turbocharger tube with a CM / reinforcing layer AR / CM structure.

[0129] Comparative Example 1

[0130] This comparative example provides a chlorinated polyethylene rubber material, which differs from Example 1 in that: no composite anti-scorching agent is added to the chlorinated polyethylene rubber material;

[0131] The preparation method of this chlorinated polyethylene rubber material is the same as that in Example 1.

[0132] Comparative Example 2

[0133] This comparative example provides a chlorinated polyethylene rubber material, which differs from Example 1 in that: in the composite anti-scorching agent, a single antioxidant is used, and only hindered phenol 168 is added;

[0134] The preparation method of this chlorinated polyethylene rubber material is the same as that in Example 1.

[0135] Comparative Example 3

[0136] This comparative example provides a chlorinated polyethylene rubber material, which differs from Example 1 in that: benzenesulfonamide EC-80 is not added to the composite anti-scorching agent;

[0137] The preparation method of this chlorinated polyethylene rubber material is the same as that in Example 1.

[0138] Comparative Example 4

[0139] This comparative example provides a chlorinated polyethylene rubber material, which uses a peroxide vulcanization system and comprises the following components by weight percentage:

[0140] 100 parts chlorinated polyethylene rubber (CH-430), 40 parts carbon black (N550), 15 parts filler (N85), 35 parts plasticizer (TOTM), 12 parts magnesium oxide, 3 parts flow aid (WB222), 2 parts peroxide BIPB-40, 3 parts peroxide DBPH-45 and 3 parts accelerator TAC-70.

[0141] The preparation process of this chlorinated polyethylene rubber material includes:

[0142] The chlorinated polyethylene rubber, carbon black, filler, plasticizer, magnesium oxide and flow aid in the formula are put into the internal mixer in sequence. The mixing temperature is not higher than 120℃, the mixing pressure is 4MPa and the mixing time is 7 minutes. The mixture is mixed once to obtain a first-stage compound.

[0143] Then, oxides BIPB-40 and DBPH-45 and accelerator TAC-70 are added, and a second mixing is carried out. The mixing temperature is not higher than 100℃, the mixing pressure is 4MPa, and the mixing time is 3 minutes. The chlorinated polyethylene rubber material is obtained.

[0144] Compare and contrast examples 1-4

[0145] This comparative application example provides a turbocharger pipe. Comparative application examples 1-4 use the CM rubber material prepared by comparative examples 1-4 as the preparation material for the inner rubber layer and the outer rubber layer, respectively. The preparation process of comparative application examples 1-4 is the same as that of application example 1.

[0146] Test case

[0147] Performance testing:

[0148] (1) The Mooney scorch of the CM rubber compounds prepared in Examples 1-10 and Comparative Examples 1-4 was tested according to GB / T1233-2008, and the Mooney viscosity was tested according to GB / T 1232.1-2016.

[0149] (2) Following the TL52648 standard method, strip-shaped samples were prepared using the outer rubber grinding discs of Application Examples 1-10 and Comparative Application Examples 1-4, and tested in an ozone meter. The sample size was 10mm × 100mm × 1.5mm, and the high ozone concentration was 200pphm.

[0150] (3) Using the turbocharger pipes of Application Examples 1-10 and Comparative Application Examples 1-4, the odor was evaluated according to the odor test standard for components inside the PV3900 automobile. The evaluation level table of the odor test standard for components inside the PV3900 automobile is shown in Table 1.

[0151] Table 1. Evaluation Level Table

[0152] Score evaluate 1 Unable to feel 2 Perceptible, unobstructed 3 It's noticeable, but not a major hindrance. 4 Obstacles 5 Significantly hindered 6 Unbearable

[0153] The test results are shown in Tables 2 and 3.

[0154] Table 2

[0155]

[0156] As shown in Table 1, the Mooney scorch time ranged from 7:35 to 19:38 in Examples 1-10, indicating that these formulations had moderate scorch times, were less prone to scorching during processing, and exhibited good process stability. The scorch time of Comparative Example 1 (without composite anti-scorch agent) was only 5:43, significantly lower than most examples, indicating that not adding the composite anti-scorch agent significantly reduced the scorch time, leading to poor process stability. The scorch time of Comparative Example 4 (peroxide system) was 23:12, significantly higher than Examples 1-10, but this was due to the low reactivity and slow vulcanization rate of the peroxide vulcanization system itself, not due to the anti-scorch agent. However, the peroxide system still had problems such as poor ozone aging performance and strong odor. It is evident that the introduction of the composite anti-scorch agent effectively extended the scorch time and improved processing safety; while the formulation combining the thiadiazole vulcanization system with the composite anti-scorch agent performed well in terms of scorch time control.

[0157] The Mooney viscosity of the materials in Examples 1-10 ranged from 64.44 to 75.36, which is generally within a reasonable range, indicating that the rubber compound has good plasticity and processing performance. Comparative Example 1 (without composite anti-scorching agent): The Mooney viscosity was as high as 88.03, indicating that the rubber compound was relatively hard and difficult to process, possibly related to uneven vulcanization or structural changes caused by scorching. Comparative Example 4 (peroxide system): The Mooney viscosity was 77.78, slightly higher than most of the examples.

[0158] Table 3

[0159]

[0160]

[0161] Table 2 shows that, regarding ozone resistance performance analysis, Application Examples 1-10 (based on the turbocharger pipes of Examples 1-10) did not exhibit cracking in either static or dynamic ozone resistance tests, indicating that the formulation design using a thiadiazole vulcanization system combined with a composite anti-scorching agent significantly improved ozone resistance. In contrast, Application Example 4 (based on Comparative Example 4, using a peroxide vulcanization system) showed cracking in both static and dynamic ozone resistance tests, indicating that the peroxide vulcanization system has poor aging resistance under high ozone conditions.

[0162] Mechanical property analysis: The tensile strength of Application Examples 1-10 ranges from 13.8 to 16.5 MPa, and the elongation at break ranges from 411% to 523%, indicating that the material has good mechanical properties and meets the application requirements of turbocharger pipes. Among them, Application Examples 1-3 have better overall mechanical properties. In contrast, the absence of benzenesulfonamide in Application Example 3 resulted in a decrease in mechanical properties. Furthermore, Application Examples 1 and 7-8 show that turbocharger pipes using composite anti-scorching agents with specific formulation components have better overall mechanical properties.

[0163] Odor evaluation analysis: The odor evaluation scores of Application Examples 1-10 ranged from 3.0 to 3.5, indicating that the formulations using the thiadiazole vulcanization system performed well in terms of odor, meeting the low odor requirements for automotive interior components. In contrast, Application Example 4 (based on Comparative Example 4, using a peroxide vulcanization system) had an odor evaluation score of 4.0, indicating that its odor was poor.

[0164] In contrast, the absence of a composite anti-scorching agent in Application Example 1 resulted in poor process stability and made production impossible; in contrast, the use of only a single antioxidant in Application Example 2 led to a decrease in ozone resistance.

[0165] The chlorinated polyethylene rubber material provided by this invention introduces a composite anti-scorching agent and a thiadiazole vulcanization system, resulting in products with excellent ozone resistance, good mechanical properties, and low odor. This invention effectively solves the problems of scab formation, poor ozone resistance, and poor odor during the vulcanization process in the prior art.

[0166] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A chlorinated polyethylene rubber material, characterized in that, Its components include: chlorinated polyethylene rubber, composite anti-scorching agent, alkaline metal oxide, thiadiazole vulcanizing agent and amine accelerator; The composite anti-scorching agent comprises: N-cyclohexylthiophthalimide, benzenesulfonamide, and antioxidant.

2. The chlorinated polyethylene rubber material according to claim 1, characterized in that, The alkaline metal oxide includes one or both of magnesium oxide and zinc oxide; Preferably, the thiadiazole vulcanizing agent includes one or more of JY-75, PT75, TDD, TDDS, and the composite vulcanizing agent H631; Preferably, the amine accelerator includes one or both of JY719 and accelerator 903.

3. The chlorinated polyethylene rubber material according to claim 1, characterized in that, The components of the chlorinated polyethylene rubber material also include: carbon black, filler, plasticizer, and flow aid; Preferably, the filler comprises one or both of N85 and H1010; Preferably, the plasticizer includes one or more of TOTM, epoxy fatty acid methyl esters, and citrate esters; Preferably, the flow aid includes one or both of WB222 and LP-54; Preferably, the antioxidant includes hindered phenolic antioxidants and / or phosphite antioxidants.

4. The chlorinated polyethylene rubber material according to claim 3, characterized in that, The components of the chlorinated polyethylene rubber material, by weight fraction, include: 100 parts chlorinated polyethylene rubber, 30-50 parts carbon black, 10-20 parts filler, 30-50 parts plasticizer, 0.5-1.5 parts composite anti-scorching agent, 6-15 parts alkaline metal oxide, 1-5 parts flow aid, 1.0-3.0 parts thiadiazole vulcanizing agent, and 0.5-1.5 parts amine accelerator.

5. The chlorinated polyethylene rubber material according to claim 3, characterized in that, The composite anti-scorching agent comprises, by weight percentage: 30%–40% benzenesulfonamide, 20%–30% hindered phenolic antioxidant, 15%–25% phosphite antioxidant, and the balance N-cyclohexylthiophthalimide.

6. The method for preparing chlorinated polyethylene rubber material according to any one of claims 1-5, characterized in that, Includes the following steps: (a) A mixture of chlorinated polyethylene rubber, composite anti-scorching agent and alkaline metal oxide is mixed once to obtain a compound rubber. (b) Add thiadiazole vulcanizing agent and amine accelerator to the first-stage compound and perform secondary mixing to obtain the chlorinated polyethylene rubber material.

7. The preparation method according to claim 6, characterized in that, The preparation process of the composite anti-scorching agent includes: mixing N-cyclohexylthiophthalimide, benzenesulfonamide and antioxidant to obtain the composite anti-scorching agent; Preferably, the mixture in step (a) further includes carbon black, filler, plasticizer and flow aid.

8. The application of the chlorinated polyethylene rubber material as described in any one of claims 1-5 or the chlorinated polyethylene rubber material prepared by the preparation method described in claim 6 or 7 in the preparation of turbocharger pipes.

9. A turbocharger pipe, characterized in that, include: Inner adhesive layer, reinforcing layer, and outer adhesive layer; The materials of the inner rubber layer and the outer rubber layer both include the chlorinated polyethylene rubber material according to any one of claims 1-5 or the chlorinated polyethylene rubber material prepared by the preparation method according to claim 6 or 7. The reinforcing layer is disposed on the outside of the inner adhesive layer, and the outer adhesive layer is disposed on the outside of the reinforcing layer.

10. The turbocharger pipe according to claim 9, characterized in that, The reinforcing layer is made of aramid yarn; Preferably, the preparation process of the turbocharger pipe includes: forming an inner rubber layer by extrusion using chlorinated polyethylene rubber material, then forming a reinforcing layer by knitting aramid yarn on the inner rubber layer, and then forming an outer rubber layer by extrusion using chlorinated polyethylene rubber material on the surface of the reinforcing layer; Preferably, after forming the inner adhesive layer, the reinforcing layer, and the outer adhesive layer, cooling is performed to obtain the tube blank; Preferably, the tube blank is vulcanized to obtain a turbocharger tube.

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